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Open-air oxidative Heck reactions at room temperature
Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry.
Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry.
Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry.
Uppsala University, Disciplinary Domain of Medicine and Pharmacy, Faculty of Pharmacy, Department of Medicinal Chemistry, Organic Pharmaceutical Chemistry.
2006 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 8, no 4, 338-343 p.Article in journal (Refereed) Published
Abstract [en]

Palladium(II)-catalyzed oxidative Heck arylation reactions proceed at room temperature with atmospheric air as the sole reoxidant. Using arylboronic acids as arylating agents and inexpensive 2,9-dimethyl-1,10-phenanthroline as the supporting ligand, efficient vinylic substitution reactions were obtained both with electron-poor and electron-rich olefins on a 1–50 mmol scale.

Place, publisher, year, edition, pages
2006. Vol. 8, no 4, 338-343 p.
National Category
Medical and Health Sciences
Identifiers
URN: urn:nbn:se:uu:diva-94792DOI: 10.1039/B517152KOAI: oai:DiVA.org:uu-94792DiVA: diva2:168775
Available from: 2006-09-14 Created: 2006-09-14 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Novel Metal-Mediated Organic Transformations: Focusing on Microwave Acceleration and the Oxidative Heck Reaction
Open this publication in new window or tab >>Novel Metal-Mediated Organic Transformations: Focusing on Microwave Acceleration and the Oxidative Heck Reaction
2006 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Transition metals have played an important role in synthetic organic chemistry for more than a century, and offer catalytic transformations that would have been impossible with classical chemistry. One of the most useful and versatile of the transition metals is palladium, which over the years has catalyzed many important carbon-carbon forming reactions. Popular cross-coupling reactions such as the Suzuki, Stille and the Heck reaction are all catalyzed by palladium, or more correctly, by palladium in its ground state, Pd(0).

Recently, interest in palladium(II)-catalyzed transformations has started to grow, partly due to the development of the vinylic substitution reaction, commonly called the oxidative Heck reaction, presented in this thesis. This Pd(II)-catalyzed, ligand-modulated reaction occurs under air at room temperature, and for the first time a general protocol employing a wide range of olefins and arylboronic acids was obtained. Ligand screening showed that the bidentate nitrogen ligand, 2,9-dimethyl-1,10-phenanthroline (dmphen), was the most suitable ligand. Dmphen is believed to facilitate regeneration of active Pd(II), increase catalytic stability and improve the regioselectivity in the reaction. A mechanistic investigation was conducted using electrospray ionization mass spectrometry (ESI-MS), making it possible to observe cationic intermediates in a productive oxidative Heck arylation. The results obtained are in agreement with the previously proposed catalytic cycle.

The emerging discipline of high-speed synthesis is making contributions to society’s growing demand for new chemical entities. This inspired the development of two ultrafast, microwave-accelerated carbonylation reactions with dicobalt octacarbonyl acting both as an in situ carbon monoxide supplier and reaction mediator. A wide range of symmetrical benzophenones was produced in only 6 to 10 s, using aryl iodides as the substrate. The second carbonylation reaction provided symmetrical and unsymmetrical ureas in process times ranging from 10 s to 40 minutes using primary and secondary amines.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2006. 77 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Pharmacy, ISSN 1651-6192 ; 37
Keyword
Organic chemistry, palladium(II), oxidative Heck reaction, high-throughput-chemistry, microwave acceleration, dicobalt octacarbonyl, in situ carbonylation, urea, diaryl ketones, ESI-MS, Organisk kemi
Identifiers
urn:nbn:se:uu:diva-7117 (URN)91-554-6638-9 (ISBN)
Public defence
2006-10-06, B41, BMC, Husargatan 3, Uppsala, 09:15
Opponent
Supervisors
Available from: 2006-09-14 Created: 2006-09-14Bibliographically approved

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Lindh, JonasLarhed, Mats

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